Thermal cracking of alpha, beta-dichloro-propionitrile



United States Patent Otilice 3,,llb9fl58 Patented Dec. 18, 1952 The present invention relates to B-chloroacrylonitrile. More particularly, this invention relates to a novel method for the preparation of ,8-chloroacrylonitrile.

It is known that B-chloroacrylonitrile or Z-chloro-vinyl cyanide (ClCl-l CH-CN) may possibly be obtained as a by-product of the catalytic vapor phase chlorination of acrylonitrile at temperatures between about 200 C. and 550 C. However, since the principal product, occhlo-roacrylonitrile or l-chlorovinyl cyanide is only produced in an amount of about 40% based upon the reacted acrylonitrile the process does not afford too suitable 2. method for the preparation of ,B-chloroacrylonitrile.

Another method which has been employed for the preparation of fi-chloroacrylonitrile involves the reaction of acetylene with cyanogen chloride. The use of certain catalysts such as cuprous chloride and alkali and alkalineearth metal cyanides is preferred in such a method in order to obtain somewhat better yields than those resulting merely from the reaction of cyanogen chloride and acetylene in an inert solvent such as hexane.

in any event, however, neither known method for the production of fl-chloroacrylonitrile may be considered to be especially advantageous since the former method, at best, affords only small yields of B-chloroacrylonitrile while the latter process, although an improvement to some degree over the former, nonetheless provides low yields and conversions.

In view of t.e disadvantages of the methods of the prior art, the need ha long existed for a simple process for the preparation of [3-chloro-acrylonitrile. The desirability of such a process has become more significant since fi-chloroacrylonitrile is particularly useful in the formation of resinous and rubber like copclymers with LS-butadiene, acrylonitrile, styrene and other like ethylenically unsaturated compounds. Moreover, Bcl1loroacrylonitrile may be readily hydrolyzed in a co-nven tionsl procedure to produce ,d-chloroacrylic acid and may be hydrogenated to yield B-chloropropionitrile which in turn may be dehydrochlorinated to acrylonitrile. Additional uses for fl-chloroacrylon ile will also be readily apparent to those killed in the art.

it has now been discovered that B-chloroacrylonitrile may be readily prepared excellent yield by thermally cracking a,,6-dichloropropicnitrile at certain preferred temperature conditions. In accordance with the present invention, a o dichloropropionitrile, which is obtained as a reaction product of acrylonitrile and chlorine, is subjected to temperatures in excess of 475 C. for a minimum period of actual contact time. The resultant B- chioroacrylonitrile is then easily distilled or otherwise separated from the crude reaction mixture. As a result of our simple expeditious process B-chloroacrylonitrile is obtained in markedly improved yield as compared with that of prior art processes and is substantially free of contaminating by-products resulting from the pyrolysis rocedure.

The temperature at which d-dichloropropionitrile is pyrolyzed is critical only insofar as it should be at least 475 C. Below 475 C., only relatively small amounts of fichloroacrylonitrile are produced. However, at thermal cracking temperatures above 475 C.

surprisingly 0:,8-dichloropropionitrile readily is dehydrochlorinated to yield amounts of from about 30 to about 65% of B-chloroacrylonitrile, based upon the weight of a,,8dichloropropionitt'ile starting material. In general, cracking temperatures of from about 475 C. to about 706 C. are satisfactory and no particular advantage is apparently seen to be derived from employing temperatures above about 700 C. Preferably, however, pyrolysis temperatures of from about 550 C. to about 650 C. are employed for optimum yield. While the thermal cracking of e it-diehloropropionitrile may be accomplished merely by subjecting the same: to temperatures in excess of about 475 C. it is also within the scope of this invention to employ a catalyst, e.g., one of the weakly acidic or neutral absorbent types, in the process but the use or" such catalysts is not absolutely necessary since the present pyrolysis procedure affords high yields of ,o-chloroacrylonitrile even Without the use of catalytic masses.

The thermal cracking or pyrolysis may be carried out in any suitable pyrolytic reaction apparatus which will afford proper temperature control, for example, in a heated tube. Such a heated tube may be constructed of thermally resistant glass, quartz or the like. Prolonged preheating of the starting material, oafi-CllChlOIO- propionitrile should be avoided. Otherwise, substantial amounts of a-c loroacrylonitrile may be obtained. It generally de rable to vent the hydrogen chloride liberated from the cracked afi-dicbloropropionitrile since it it is allowed to remain in contact with the ,B-chloroacrylonitrile it may possibly cause regeneration of s edichloropropionitrile. Collection of the products may be accomplished by any convenient and desirable means, e.g., a series of ice traps and/or suitable solvent vessels. it may sometimes be necessary to add an inhibitor or mild neutralizing agent to the product collection trap in order to forestall or retard polymerization of the products or regeneration of a,B-dichloropropionitrile. The crude reaction mixture may be readily separated, e.g., by fractional distillation, to yield the desired fi-chloroacrylonitrile. Both a.-chloro-acrylonitrile which is also obtained and may be recombined with hydrogen chloride to form a,/3--dichloropropionitrile and unreacted u,fi-dichloropropionitrile may be subsequently recycled through the reactor.

The starting material, e p-(llchloropropionitrile, is readily prepared by reaction of chlorine and acrylonitrile preferably in the presence of a solvent such a pyridine at temperatures of from about 10 to about 50 C. Of course, other methods for the preparation or" 0c,fidlchloropropionit ile are well known and these include the reactions of chlorine and acrylonitrile at room temperature in the presence of lig t both in the presence of and in the absence of a solvent.

Examples of preferred methods of practicing our in vention are set forth hereinafter but it is to be understood that the examples are merely illustrative and are not to be construed as limiting the scope of this invention.

Example 1 into a bo-rosilicate glass tube (42 mm. x 40 cm.) maintained at a. temperature of 605 C. is ted 3880 grams of a,,G-dichloropropicnitrile at the rate of grams/hour. The liquid products are collected in a trap at 25 C. and the gaseous materials such as hydrogen chloride are vented to the atmosphere. Vapor phase chromatographic analysis shows the ratio of materials in the crude product to be: B-chloroacrylonitrile: 63; otchloroacr lonitrile: 31; wfi-dichloropropionitrile: 5. The ratio of fi-chloroacrylonitrile to a-chloroacrylonitrile is thus 2.0/ On distillation there is isolated 920 grams (33%) ,B-chloroacrylonitrile B.P. 117l44 C. and 405 grams of u-chloroacrylonitrile Bl 8790 C.

The procedure of Example I is followed and results obtained in the various runs wherein different conditions are employed appear in the following table:

propionitrile at a temperature in exces of about 475 C. and recovering ,B-chloroacrylonitrile.

2. A method for preparing fi-chloroacrylonitrile which consists essentially of heating a,,8-dichloropropionitrile to a temperature within the range of from about 475 a, B-Dichloropropionitrilc iced Vapor phase chromatographic analysis of crude product Ratio of B- chloroacry- Example lonitrile to Reactor Rate of Contact B-Chloroa-Chloroa,fl-Dichloa-chloroaery- Size of reactor Grams temp, 0. feed, grams/ time, Sec-s. acryloniacryloniropropiolonitrile in hour trile trile nitrile product 2. 28 mm. cm... 400 27 15 21 27 44 .8/1. 0 l 75 465 8 42 30 32 37 .9/1. 0 75 495 8 44 52 39 9 1.3/1.0 75 525 8 46 56 38 7 1.5/1.0 75 555 13 31) 59 37 4 1. 6/1. 0 400 575 21 60 33 7 1.8/1. 0 400 590 17 64 32 5 2.0/1.0 400 600 130 21 6O 34 3 1.8/1.0 400 620 20 62 35 3 1.8/1.0

From the results appearing in the examples hereinabove it will be observed that when the pyrolysis of ,5- dichloropropiouitrile is conducted within the preferred critical temperature ranges, the ratio of fi-chloroacrylonitrile to a-chloroacrylonitrile varies from about 1.3 to about 2.0 of the B-compound to 1.0 of the OL-COmPQllnd- Below temperatures of about 475 0., however, onchloroacrylonitrile is preferentially obtained. Thus, the thermal cracking of a,fi-dichloropropionitrile affords an easy method for production of B-cnloroacrylonitrile in yields hitherto not considered possible.

We claim:

1. A method for preparing B-chloroacrylonitrile which consists essentially of thermally crackling a,fi-dichloro- References Cited in the file of this patent UNITED STATES PATENTS Long Feb. 11, 1941 Lichty et al Get. 13, 1942 Cliiford et al Mar. 16. 1948 OTHER REFERENCES Brintzinger et aL: Angew. Chem., A60, pages 311-621 (1948). 

1. A METHOD FOR PREPARING B-CHLOROACRYLONITRILE WHICH CONSISTS ESSENTIALLY OF THERMALLY CRACKING A,B-DICHLOROPROPIONITRILE AT A TEMPERATURE IN EXCESS OF ABOUT 475* C. AND RECOVERING B-CHLOROACRYLONITRILE. 